Microparticles, external additive for toner, toner, two-component developer, and method for producing toner

Abstract

To provide fine particles that have electrification stability even when images are output for a long period in a high temperature and high humidity environment and a low temperature and low humidity environment, and exhibit good image density, image density uniformity, and image quality.SOLUTION: In fine particles of a silicon polymer having a siloxane bond and a silanol group, the amount of water adsorbed in the fine particles at a temperature of 30°C and a humidity of 80%RH is 1.0 mg / g or more and 22.0 mg / g or less; the amount of a silanol group in the fine particles measured by a titration method using KOH is 0.012 mmol / g or more and 0.120 mmol / g or less; the number average particle diameter of primary particles of the fine particles is 0.05 μm or more and 0.30 μm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to fine particles, an external additive for a toner, a toner used in an electrophotographic system, a two-component developer using the toner, and a method for producing the toner. [Background technology]

[0002] In recent years, with the widespread use of electrophotographic full-color copiers, there has been an increasing demand for toners used in electrophotography that can handle higher printing speeds, and that are environmentally stable and have a longer lifespan. Conventionally, silica has been widely used as an external additive in toners. Generally, there have been reports of silica obtained by a dry or wet method (sol-gel method) being surface-treated to enhance its hydrophobicity. For example, Patent Document 1 discloses an example in which highly hydrophobic spherical sol-gel silica microparticles are added to toner base particles to improve the charging stability of the toner. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-099582 [Patent Document 2] International Publication No. 2015 / 107961 [Patent Document 3] Japanese Patent Application Publication No. 2018-004949 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when images are output in a high-temperature, high-humidity environment over a long period of time, the silica present on the toner surface is affected by moisture, reducing the toner charge, which can result in reduced image density and image density uniformity, or in failure to obtain high-quality images. Furthermore, when images are output in a low-temperature, low-humidity environment over a long period of time, the silica present on the toner surface can be affected by humidity, causing the toner to become overcharged. In this case, the toner becomes less likely to fly from the developing unit, which can result in reduced image density and image density uniformity, or in failure to obtain high-quality images. Thus, when image output environments differ, there is still room for improvement in terms of image density, image density uniformity, and image quality, which are due to the toner's charge stability. On the other hand, as in Patent Documents 2 and 3, there are examples in which polyalkylsilsesquioxane fine particles are added to toner particles to improve the fluidity and charging stability of the toner. However, it has been found that in the techniques of any of the above documents, when images are output over a long period of time in a high-temperature, high-humidity environment or a low-temperature, low-humidity environment, there is room for improvement in terms of image density, image density uniformity, and image quality, which are caused by the charging stability of the toner.

[0005] The present disclosure provides fine particles, an external additive for a toner, a toner, a two-component developer, and a method for producing a toner that have charge stability and good image density, image density uniformity, and image quality even when images are output over a long period of time under high-temperature, high-humidity environments and low-temperature, low-humidity environments. [Means for solving the problem]

[0006] The present disclosure provides fine particles of a silicon polymer having siloxane bonds and silanol groups, the water adsorption amount of the microparticles at a temperature of 30°C and a humidity of 80% RH is 1.0 mg / g or more and 22.0 mg / g or less; the amount of silanol groups in the fine particles measured by a titration method using KOH is 0.012 mmol / g or more and 0.120 mmol / g or less, The number-average particle size of the primary particles of the fine particles is 0.05 μm or more and 0.30 μm or less.

[0007] The present disclosure also relates to an external toner additive containing the fine particles. The present disclosure also relates to a toner having toner particles and the external toner additive. The present disclosure also relates to a two-component developer having the above toner and a magnetic carrier. The present disclosure also provides a method for producing the toner, the method comprising: a mixing step of mixing the toner particles with the external toner additive to obtain a toner particle mixture; and a heat treatment step of heat treating the toner particle mixture. [Effects of the Invention]

[0008] The present disclosure provides fine particles, an external additive for a toner, a toner, and a two-component developer that have charge stability and provide good image density, image density uniformity, and image quality even when images are output over a long period of time under high-temperature, high-humidity environments and low-temperature, low-humidity environments. [Brief explanation of the drawings]

[0009] [Figure 1] Examples of heat treatment equipment DETAILED DESCRIPTION OF THE INVENTION

[0010] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0011] The present inventors believe that the mechanism by which the above effects are exhibited is as follows. The fine particles are characterized by their low moisture adsorption at a temperature of 30°C and a humidity of 80%RH. Because the fine particles are less likely to adsorb moisture in a high-temperature, high-humidity environment, a decrease in the toner charge can be suppressed. Therefore, the toner maintains charge stability over a long period of time in a high-temperature, high-humidity environment, resulting in good image density, image density uniformity, and image quality.

[0012] Furthermore, the microparticles are characterized by a moderate amount of silanol groups present on their surfaces, despite their low moisture adsorption at a temperature of 30°C and a humidity of 80% RH. The silanol groups leak excess charge from the toner, preventing excessive charging of the toner in low-temperature, low-humidity environments. This results in good charge stability, image density, image density uniformity, and image quality over long periods of time in low-temperature, low-humidity environments.

[0013] Sol-gel silica particles and polyalkylsilsesquioxane particles, which have traditionally been used as external toner additives, are particles primarily composed of siloxane bonds (Si-O-Si). Sol-gel silica particles and polyalkylsilsesquioxane particles typically have silanol groups at their terminals, resulting in unreacted silanol groups remaining on the particle surface and inside. Because silanol groups readily adsorb moisture, they adsorb a large amount of moisture at a temperature of 30°C and a humidity of 80% RH. Therefore, in high-temperature, high-humidity environments, the particles adsorb moisture, reducing the toner's charge.

[0014] One method to address this issue is to trimethylsilylate (surface treatment) the residual silanol groups by subjecting them to a coupling reaction with a silane compound or the like, thereby reducing the amount of moisture adsorption. However, because sol-gel silica particles originally have a large amount of residual silanol groups, even after surface treatment, the amount of residual silanol groups is still large, resulting in a large amount of moisture adsorption at a temperature of 30°C and a humidity of 80% RH. Therefore, in a high-temperature, high-humidity environment, the particles adsorb moisture, reducing the toner's charge. Furthermore, the amount of silanol groups on the surface of polyalkylsilsesquioxane microparticles can be reduced by surface treatment, and the amount of water adsorption at a temperature of 30°C and a humidity of 80% RH can be reduced. However, if the amount of water adsorption is sufficiently reduced, the amount of silanol groups on the surface will also be reduced. Therefore, the toner becomes excessively charged in a low-temperature, low-humidity environment.

[0015] The fine particles satisfying the above-mentioned characteristics have a low moisture adsorption amount at a temperature of 30°C and a humidity of 80% RH, and a large amount of silanol groups present on the surface. Therefore, it is possible to provide fine particles, an external toner additive, and a toner that have charge stability, good image density, good image density uniformity, and good image quality even when images are output over a long period of time under high-temperature, high-humidity environments and low-temperature, low-humidity environments.

[0016] The water adsorption amount of the microparticles at a temperature of 30°C and a humidity of 80% RH is 1.0 mg / g or more and 22.0 mg / g or less, preferably 2.0 mg / g or more and 15.0 mg / g or less, more preferably 3.0 mg / g or more and 12.0 mg / g or less, even more preferably 4.0 mg / g or more and 9.5 mg / g or less, and even more preferably 4.5 mg / g or more and 9.0 mg / g or less.

[0017] When the moisture adsorption amount is within the above range, the fine particles are less likely to adsorb moisture in a high-temperature, high-humidity environment, and therefore the decrease in the charge amount of the toner can be suppressed, resulting in good charge stability, image density, image density uniformity, and image quality over a long period of time in a high-temperature, high-humidity environment.

[0018] The amount of silanol groups in the fine particles measured by titration using KOH is 0.012 mmol / g or more and 0.120 mmol / g or less, preferably 0.012 mmol / g or more and 0.100 mmol / g or less, and more preferably 0.014 mmol / g or more and 0.050 mmol / g or less.

[0019] The specific method for the titration method using KOH will be described later, but the amount of silanol groups measured by this titration method represents the amount of silanol groups present on the surface of the fine particles. When the amount of silanol groups measured by the titration method using KOH of the fine particles is within the above range, excessive charging of the toner can be suppressed in a low-temperature, low-humidity environment. Therefore, charging stability can be maintained over a long period of time in a low-temperature, low-humidity environment, resulting in good image density, image density uniformity, and image quality.

[0020] Conventional toner additives, such as silica particles and organosilicon polymer particles, have been surface-treated to reduce the amount of moisture adsorbed at a temperature of 30°C and a humidity of 80%. However, this reduces the amount of silanol groups on the surface, making the toner more susceptible to excessive charging in low-temperature, low-humidity environments. In contrast, the microparticles of the present disclosure can reduce water adsorption while controlling the amount of silanol groups on the surface within an appropriate range by adjusting the ratio of silane monomers (described below). Conventional organosilicon polymer microparticles have a high ratio of trifunctional silanes, while conventional sol-gel silica microparticles have a high ratio of tetrafunctional silanes. Therefore, surface treatment is necessary to reduce water adsorption.

[0021] On the other hand, increasing the proportion of bifunctional silanes or monofunctional silanes makes it possible to reduce the amount of water adsorption on the microparticles. It was also found that increasing the proportion of bifunctional silanes or monofunctional silanes reduces the amount of silanol groups on the surface. By increasing the proportion of bifunctional silanes or monofunctional silanes and using tetrafunctional silanes or trifunctional silanes, it became possible to achieve both the amount of water adsorption and the amount of silanol groups on the microparticles within desirable ranges not previously possible.

[0022] The number average particle size of the primary particles of the fine particles is 0.05 μm or more and 0.30 μm or less. The number average particle size of the primary particles of the fine particles is preferably 0.07 μm or more and 0.20 μm or less. It is more preferable that the thickness is 0.08 μm or more and 0.18 μm or less.

[0023] When the number-average particle diameter of the primary particles of the fine particles is within the above range, the external additive can be easily coated uniformly on the toner particles. Furthermore, stress on the toner can be suppressed, which makes it easier to obtain the effect of charge stability. Therefore, the image density, image density uniformity, and image quality are improved over a long period of time under high-temperature, high-humidity environments and low-temperature, low-humidity environments.

[0024] The method for producing silicon polymer microparticles is not particularly limited, but it is preferable to form the microparticles by hydrolysis of a silicon compound (silane monomer) using a sol-gel method and a polycondensation reaction. Specifically, it is preferable to form the microparticles by polymerizing a mixture containing a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds through hydrolysis and a polycondensation reaction. Silane monomers such as bifunctional silane and tetrafunctional silane will be described later.

[0025] That is, the silicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of bifunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. The proportion of bifunctional silane is preferably 50 mol% to 73 mol%, more preferably 54 mol% to 70 mol%, and even more preferably 61 mol% to 65 mol%. The proportion of tetrafunctional silane is preferably 27 mol% to 50 mol%, more preferably 30 mol% to 46 mol%, and even more preferably 35 mol% to 39 mol%.

[0026] The present inventors have found that the ratios of the bifunctional silane and tetrafunctional silane are important in the method for producing microparticles. By controlling the ratios of the bifunctional silane and tetrafunctional silane within the above ranges, it becomes easier to control both the moisture adsorption amount at 30°C and 80% RH and the amount of silanol groups in the microparticles measured by titration with KOH within preferred ranges. Furthermore, by adding a monofunctional silane and a trifunctional silane in addition to the bifunctional silane and tetrafunctional silane, it is possible to adjust the moisture adsorption amount at 30°C and 80% RH and the amount of silanol groups in the microparticles measured by titration with KOH.

[0027] In addition to the mixing ratio of the above monomers, the amount of water adsorption at a temperature of 30°C and a humidity of 80% RH and the amount of silanol groups measured by titration using finely divided KOH particles can also be adjusted by adjusting the solvent temperature during the hydrolysis and condensation reaction (e.g., the temperature in the condensation polymerization step), the type of catalyst, the stirring time, the pH of the solution, etc. The amount of water adsorption can be increased by lowering the stirring temperature in the condensation step, and can be decreased by raising the stirring temperature in the condensation step. Furthermore, for example, the amount of silanol groups on the surface of the microparticles can be increased by lowering the stirring temperature in the condensation polymerization process or by reducing the amount of catalyst, and can be decreased by raising the stirring temperature in the condensation process or by increasing the amount of catalyst.

[0028] The fine particles and external toner additives contain silicon polymer particles having siloxane bonds, and the silicon polymer particles preferably contain 90% by mass or more, more preferably 95% by mass or more of silicon polymer.

[0029] The method for producing silicon polymer particles is not particularly limited; for example, a silane compound is dropped into water, hydrolyzed and condensed in the presence of a catalyst, and the resulting suspension is then filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction initiation temperature, the dropwise addition time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide, but are not limited to these. It will not be done.

[0030] Silicon polymer particles are preferably produced by the following method.Specifically, it is preferable to include the following steps: a first step of obtaining a hydrolyzate of a silicon compound; a second step of mixing the hydrolyzate with an alkaline aqueous medium to cause a polycondensation reaction of the hydrolyzate; and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles.In some cases, a hydrophobic agent may be further added to the spherical silicon polymer particle dispersion to obtain hydrophobic spherical silicon polymer particles.

[0031] In the first step, a silicon compound is contacted with a catalyst by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. Known catalysts can be suitably used. Specific examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0032] The amount of catalyst used may be adjusted appropriately depending on the type of silicon compound and catalyst. Preferably, the amount of catalyst used is 1×10 -3 The amount is selected in the range of 1 part by mass to 1 part by mass.

[0033] The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of silicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if it is 15 moles or less, productivity will be improved.

[0034] The reaction temperature is not particularly limited and may be carried out at room temperature or under heating, but it is preferable to carry out the reaction at a temperature maintained at 10 to 60° C., as this allows a hydrolysate to be obtained in a short time and prevents a partial condensation reaction of the produced hydrolysate. The reaction time is not particularly limited and may be appropriately selected taking into consideration the reactivity of the silicon compound used, the composition of the reaction liquid obtained by mixing the silicon compound, acid, and water, and productivity.

[0035] In the second step of the method for producing silicon polymer particles, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursor, thereby obtaining a polycondensation reaction solution. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0036] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

[0037] The amount of the alkali component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali component, the amount is usually selected in the range of 0.01 mass % or more and 12.5 mass % or less per 100 parts by mass of the mixture of water and the organic solvent.

[0038] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is preferred.

[0039] Specific examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0040] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0041] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. Water (tap water, pure water, etc.) is preferably used as the aqueous solution, but components compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may also be added to the water. The temperatures of the polycondensation reaction liquid and the aqueous solution when mixed are not particularly limited, and are preferably selected in the range of 5 to 70°C, taking into consideration the composition, productivity, etc.

[0042] The silicon polymer particles can be recovered by any known method without any particular limitations. For example, floating powder can be scooped out, or a filtration method can be used. Filtration is preferred because of its simple operation. There are no particular limitations on the filtration method, and known devices such as vacuum filtration, centrifugal filtration, and pressure filtration can be selected. The filter paper, filters, filter cloth, etc. used in filtration are not particularly limited as long as they are industrially available, and can be selected appropriately depending on the device used.

[0043] The silicon polymer particles may be surface-treated by known means such as a silane coupling agent or silicone oil to adjust the degree of hydrophobicity.

[0044] The monomers used can be appropriately selected based on their compatibility with the solvent and catalyst, their hydrolysis properties, etc., but the preferred tetrafunctional silane is tetraethoxysilane, and the preferred bifunctional silane is dimethyldimethoxysilane.

[0045] The silicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (A). [ka]

[0046] In formula (A), R 12 , R 13 , R 14 and R 15R each independently represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2), a phenyl group, or a reactive group (for example, a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)). 12 , R 13 , R 14 and R 15 At least one of the groups is the reactive group. R 12 , R 13 , R 14 and R 15 are each independently a group having 1 to 6 carbon atoms (preferably It is preferably an alkyl group (preferably having 1 to 3 carbon atoms, more preferably 1 or 2), or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms).

[0047] To obtain silicon polymer particles, a silicon compound having four reactive groups in one molecule (tetrafunctional silane) of formula (A), R 12 is an alkyl group or a phenyl group, and three reactive groups (R 13 , R 14 , R 15 ), an organosilicon compound (trifunctional silane) having R in formula (A) 12 , R 13 is an alkyl group or a phenyl group, and two reactive groups (R 14 , R 15 ), an organosilicon compound (bifunctional silane) having R in formula (A) 12 , R 13 , R 14 is an alkyl group or a phenyl group, and one reactive group (R 15 ) can be used.

[0048] These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form crosslinked structures, resulting in silicon polymer particles. 13 , R 14 and R 15The hydrolysis, addition polymerization, and condensation polymerization can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0049] Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanate silane.

[0050] Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane. silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0051] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane. Examples include orchids.

[0052] Monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, and tripropylmethoxysilane. , tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, and the like.

[0053] The BET specific surface area of ​​the particles is 30m 2 / g or more 250m 2 / g or less, and 2 / g or more 150m 2 / g or less is more preferable. The BET specific surface area of ​​the fine particles in the above range indicates that there is a moderate amount of minute irregularities on the surface of the fine particles. The moderate amount of minute irregularities on the surface of the fine particles enhances the effect of suppressing a decrease in the charge amount of the toner over a long period of time in a high-temperature, high-humidity environment and the effect of suppressing excessive charging of the toner in a low-temperature, low-humidity environment. The BET specific surface area can be controlled by the hydrolysis and condensation conditions and the amount of catalyst.

[0054] The fine particles are preferably surface-treated with at least one compound selected from the group consisting of alkylsilazane, cyclic dimethylpolysiloxane, chlorosilane, fluorosilane, and silicone oil. The fine particles are more preferably surface-treated with alkylsilazane. By surface-treating the fine particles with the compound, the effect of suppressing the decrease in the charge amount of the toner over a long period of time in a high-temperature, high-humidity environment can be further achieved.

[0055] Examples of alkylsilazanes include hexamethyldisilazane. Examples of cyclic dimethylpolysiloxanes include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Examples of chlorosilanes include chlorotrimethylsilane and dimethyldichlorosilane. Examples of fluorine silanes include trifluoropropyltrimethoxysilane and trifluoropropyltriethoxysilane. Examples of silicone oils include dimethylsilicone oil.

[0056] of fine particles 29 In a chart obtained by Si-NMR measurement, when the total peak area corresponding to the silicon polymer is defined as A and the peak area corresponding to the structure represented by the following formula (a) is defined as S3, it is preferable that A and S3 satisfy the following formula (1). S3 / A≦0.40 (1) Furthermore, S3 / A is more preferably 0.20, more preferably 0.10, and even more preferably 0.05. There is no particular lower limit, but it is preferably 0.00 S3 / A. In structure (a), R 1 represents an alkyl group having 1 to 6 carbon atoms.

[0057] By making the particles satisfy formula (1), it is possible to suppress the decrease in the toner charge amount over a long period of time in a high-temperature, high-humidity environment, and to suppress the toner from becoming excessively charged in a low-temperature, low-humidity environment. S3 / A can be controlled by the selection of the silicon compound and the mixing ratio of the silicon compound. [ka]

[0058] of fine particles 29 In a chart obtained by Si-NMR measurement, the total peak area corresponding to the silicon polymer is A, the peak area corresponding to the structure represented by the following formula (b) is S4, and the peak area corresponding to the structure represented by the following formula (c) is S2. It is preferable that S4 satisfies the following formulas (2) and (3). 0.20≦S4 / A≦0.50 (2) 0.40≦S2 / A≦0.70 (3) Furthermore, it is more preferable that 0.30≦S4 / A≦0.46. It is even more preferable that 0.54≦S2 / A≦0.70. 2 and R 3 each independently represents an alkyl group having 1 to 6 carbon atoms.

[0059] By satisfying formulas (2) and (3), it is possible to more effectively suppress the decrease in the toner charge amount in a high-temperature, high-humidity environment over a long period of time, and to more effectively suppress the toner from becoming excessively charged in a low-temperature, low-humidity environment. S4 / A and S2 / A can be controlled by the selection of silicon compounds and the mixing ratio of the silicon compounds. [ka]

[0060] The fine particles can be used as an external toner additive. That is, the external toner additive preferably contains the above-mentioned fine particles. The toner preferably has toner particles and an external toner additive, the toner particles containing a binder resin, and the external toner additive is the above-mentioned fine particles. The content of the external toner additive in the toner is preferably 0.1 to 20.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the toner particles.

[0061] When the content of the external toner additive is 0.1 parts by mass or more, stress on the toner can be suppressed, and durability and charging stability can be improved, even when a large amount of low-density images are output over a long period of time in a harsh environment such as a high-temperature, high-humidity environment. Furthermore, when the content of the external toner additive is 20.0 parts by mass or less, filming of the external additive particles on the carrier or photosensitive material can be suppressed, even when a high-density image is output over a long period of time.

[0062] When a toner is dispersed in an aqueous medium containing a surfactant and sucrose, shaken in a shaker, and then centrifuged, the adhesion rate of the external toner additive to the toner particles (adhesion rate of the external toner additive by a water washing method) is preferably 20% or more, more preferably 30% or more. There is no particular upper limit to the adhesion rate, but it is preferably 60% or less, more preferably 50% or less.

[0063] When the adhesion rate of the external toner additive is within the above range, the external toner additive is less likely to be released from the toner even when a large amount of low-density images are output over a long period of time under a harsh environment such as a high-temperature, high-humidity environment, thereby further improving durability and charging stability. Furthermore, even when printing is performed over a long period of time under an environment in which the toner is overcharged, such as a low-temperature, low-humidity environment, the external toner additive is less likely to be released from the toner, thereby further improving the effect of suppressing overcharging of the toner. The adhesion rate of the external toner additive can be controlled by the toner manufacturing method. For example, a method in which the external toner additive is mixed with toner particles and then heat-treated can be mentioned.

[0064] <Binder resin> The binder resin used in the toner is not particularly limited, and the following polymers may be used: Examples of suitable materials include homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; and polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral resins, terpene resins, coumarone-indene resins, and petroleum-based resins. Among these, polyester resins are preferred from the viewpoints of durability and charging stability.

[0065] <Coloring agent> A colorant may be used in the toner particles. Examples of the colorant include the following: Black colorants include carbon black, and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0066] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0067] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0068] Examples of pigments for cyan toners include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments with one to five phthalimidomethyl groups substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0069] Yellow toner pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20. An example of a dye for yellow toner is CI Solvent Yellow 162. The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0070] <Wax> The toner particles may contain wax, for example: hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes containing fatty acid esters as the main component such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0071] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexyl alcohol. Examples of suitable binder resins include saturated fatty acid bisamides such as m-xylene bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacate; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and hydroxyl-containing methyl ester compounds obtained by hydrogenating vegetable oils. The wax content is preferably 2.0 to 30.0 parts by mass per 100 parts by mass of the binder resin.

[0072] <Charge control agent> The toner particles may contain a charge control agent as needed. Known charge control agents can be used, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0073] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0074] Examples of positive charge control agents include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salts in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.2 to 10 parts by mass per 100 parts by mass of the binder resin.

[0075] <Inorganic fine particles> In addition to the external toner additives described above, the toner may contain other inorganic fine particles as needed. The inorganic fine particles may be internally added to the toner particles or may be mixed with the toner particles as an external additive. When contained as an external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferred. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0076] As an external additive to improve fluidity, 2 / g or more 400m 2 In order to simultaneously improve the flowability and stabilize the durability, inorganic fine particles having a specific surface area within the above range may be used in combination as an external toner additive.

[0077] The inorganic fine particles are preferably used in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of toner particles. When the above range is satisfied, the effect of charge stability is easily obtained. The content of the external toner additive is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, of the total amount of external additives.

[0078] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to provide stable images over a long period of time, it can also be mixed with a magnetic carrier and used as a two-component developer. That is, it is preferable that the toner is the above-mentioned toner, which is a two-component developer containing a toner and a magnetic carrier.

[0079] Examples of magnetic carriers that can be used include commonly known ones such as iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state. The mixing ratio of the magnetic carrier and the toner is preferably such that the toner concentration in the two-component developer is 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

[0080] <Method of manufacturing toner particles and toner> The method for producing the toner particles is not particularly limited, and known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used.

[0081] The procedure for producing toner by the pulverization method will be described below. In the raw material mixing process, predetermined amounts of materials constituting the toner particles, such as binder resin, release agent, colorant, and optionally other components such as charge control agent, are weighed, blended, and mixed. Examples of mixing devices include a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0082] Next, the mixed materials are melt-kneaded to disperse the wax and the like in the binder resin. In this melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used, but single-screw or twin-screw extruders are the mainstream due to their advantage of allowing continuous production. Examples include a KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Co-Kneader (manufactured by Buss Co., Ltd.), and Kneedex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading is rolled using a twin roll or the like, In the cooling step, the material may be cooled with water or the like.

[0083] The cooled resin composition is then crushed to a desired particle size in a crushing process, which involves coarse crushing using a crusher such as a crusher, hammer mill, or feather mill, followed by further fine crushing using a mill such as a Cryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet type mill.

[0084] Thereafter, if necessary, the mixture is classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation) to obtain toner particles.

[0085] The resulting toner particles can be mixed with the external additive for toner and, if necessary, other external additives to obtain a toner. The toner particles and the external additives can be mixed using a mixing device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0086] In order to control the adhesion rate of the external toner additive to the toner particles by the water washing method, it is preferable to mix the external toner additive with the toner particles to obtain a toner particle mixture and then perform a heat treatment. That is, the toner manufacturing method preferably includes a mixing step of mixing the toner particles with the external toner additive to obtain a toner particle mixture, and a heat treatment step of heat-treating the toner particle mixture. For example, the heat treatment can be performed with hot air using a heat treatment device shown in FIG.

[0087] The heat treatment device has a treatment chamber 6 for heat-treating the toner particle mixture, a toner particle mixture supply means for supplying the toner particle mixture to the treatment chamber 6, a hot air supply means 7 for supplying hot air for heat-treating the toner particle mixture supplied from the toner particle mixture supply means, and a recovery means 10 for discharging the heat-treated toner particles outside the treatment chamber 6 from an outlet provided in the treatment chamber 6 and recovering them. 1 further includes a regulating means 9 as a cylindrical member, and the processing chamber 6 has a cylindrical shape that covers the outer peripheral surface of the regulating means 9. The hot air supplying means 7 is provided at one end of the cylindrical shape of the processing chamber 6 so that the hot air flows while rotating inside the cylindrical processing chamber 6. The toner particle supplying means is composed of a plurality of supply pipes 5 provided on the outer periphery of the processing chamber 6.

[0088] Furthermore, the discharge port provided in the treatment chamber 6 is provided on the outer periphery of the end of the treatment chamber 6 on the side opposite to the side where the hot air supply means 7 is provided, so as to be on an extension of the rotation direction of the toner particle mixture. Heat treatment using a heat treatment device having the above-mentioned configuration will be described below.

[0089] The toner particle mixture supplied by the raw material constant-quantity supply means 1 is introduced into an introduction pipe 3, which is installed vertically to the raw material constant-quantity supply means 1, by compressed gas adjusted by a compressed gas flow rate adjustment means 2. The mixture that passes through the introduction pipe is uniformly dispersed by a conical protruding member 4 provided in the center of the raw material constant-quantity supply means 1, and is then introduced into eight supply pipes 5 that radiate outward, and into a treatment chamber 6 where heat treatment is carried out.

[0090] At this time, the flow of the mixture supplied to the processing chamber 6 is regulated by a regulating means 9 for regulating the flow of the mixture, which is provided in the processing chamber 6. The mixture is heat-treated while swirling in the treatment chamber 6, and then cooled.

[0091] Heat for heat-treating the supplied mixture is supplied from hot air supply means 7, distributed by distribution member 12, and introduced into treatment chamber 6 by swirling member 13 for swirling the hot air in a spiral shape. The swirling member 13 for swirling the hot air has multiple blades, and the swirling of the hot air can be controlled by the number and angle of the blades. Hot air is supplied from hot air supply means outlet 11. The heat-treated toner particles are cooled by cold air supplied from the cold air supplying means 8 (cold air supplying means 8-1, 8-2 and 8-3).

[0092] Next, the cooled toner particles are collected by the collecting means 10 at the bottom end of the processing chamber. A blower (not shown) is provided ahead of the collecting means, and the toner particles are sucked and transported by the blower.

[0093] The powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same, and the recovery means 10 of the thermal sphering treatment device is provided on the outer periphery of the treatment chamber so as to maintain the swirling direction of the swirled powder particles. Furthermore, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer periphery of the device to the circumferential surface inside the treatment chamber in a horizontal and tangential direction.

[0094] After the heat-treated toner particles are obtained, the heat-treated toner particles may be mixed with various external additives using a mixer such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0095] The methods for measuring various physical properties are explained below. <Separation of external additive particles and toner particles from toner> Physical properties can also be measured using external additives separated from toner using the following method. 200 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and any clumps of toner are broken up using a spatula or similar tool.

[0096] The centrifuge tube is shaken for 20 minutes in a shaker (Iwaki Sangyo KM Shaker (model: V.SX)) at 350 strokes per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing-out rotor and centrifuged at 3500 rpm for 30 minutes.

[0097] After centrifugation, the toner is present in the top layer in the glass tube, and the external toner additive is present in the lower aqueous solution. The lower aqueous solution is sampled and centrifuged to separate the sucrose and the external toner additive, and the external toner additive is collected. If necessary, centrifugation is repeated to thoroughly separate the toner, and then the dispersion is dried and the external toner additive is collected. When multiple external toner additives are added, the external toner additives can be selected using a centrifugation method or the like.

[0098] <Method for measuring the amount of water adsorption on fine particles> The amount of water adsorption of the fine particles is measured using an adsorption equilibrium measuring device (BELSORP-aqua3: manufactured by BEL Japan Co., Ltd.). (Degassing) Before measurement, it is necessary to degas the moisture adsorbed to the sample. Attach the cell, filler rod, and cap, and weigh the empty sample. Place 0.4 g of the fine particle sample into the cell. Place the filler rod into the cell, attach the cap, and attach it to the degassing port. Once all the cells to be measured have been attached to the degassing port, open the helium valve. Turn on the button for the port to be degassed, press the "VAC" button, and degas for at least one day.

[0099] (Measurement method) Turn on the power to the measurement unit, vacuum pump, circulating water unit, and operation panel, and launch "BELaqua3.exe" (measurement software) in the center of the PC screen. Temperature control of the high-temperature air chamber: Double-click "SV" in the "TIC1" box on the "Flow Diagram" window to open the "Temperature Settings" window. Enter the temperature (80°C) and click "Set." Adsorption temperature control: Double-click "SV" in "Adsorption Temperature" on the "Flow Diagram" window and enter the "SV Value" (adsorption temperature). Click "Start Circulation" and "External Temperature Control" and click "Set." Press the "PURGE" button to stop degassing, turn the port button to OFF, remove the sample, attach the cap, weigh the sample, and then attach the sample to the main measurement unit. On the PC, click "Measurement Conditions" to open the "Measurement Condition Settings" window. The measurement conditions are as follows: Air thermostatic chamber temperature: 80.0℃ Adsorption temperature: 30.0℃ Adsorbate name: H2O Equilibrium time: 500sec Temperature waiting time: 60 min Saturated vapor pressure: 4.245kPa Sample tube pumping speed: normal Chemisorption measurement: No Initial introduction amount: 0.20cm 3 (STP)·g -1 Number of relative pressure measurement ranges: 4 Select the number of samples to be measured, enter the "measurement data file name" and "sample weight", and then start the measurement. (analysis) The analysis software attached to the measuring device is started and the water adsorption amount (mg / g) at a temperature of 30°C and a relative humidity of 80% is calculated.

[0100] <Method for measuring the amount of silanol groups in fine particles by titration using KOH> The amount of silanol groups in the fine particles is measured by a modified method of calculating the amount of silanol groups by titration based on the Sears method. (Preparing the test solution) Put 2.0 g of microparticles and 25 g of ethanol into a 200 ml beaker, shake the beaker by hand to wet the microparticles with the ethanol, add 75 g of 20% NaCl aqueous solution, and disperse the microparticles by ultrasonic dispersion for 1 minute. (measurement) The microparticle dispersion in the beaker is stirred with a stirrer. 0.1 mol / L HCl aqueous solution is added dropwise with a micropipette to adjust the pH to 4.0. 0.1 mol / L KOH solution is added dropwise as the titration solution, and the amount of 0.1 mol / L KOH added until the pH reaches 9.0 is taken as the amount of silanol groups (mmol / g). Specifically, the amount of silanol groups per unit mass of microparticles is calculated using the following formula: Amount of silanol groups (mmol / g) = Amount of KOH dropped (mmol) / 2.0 (g) (amount of fine particles in the sample)

[0101] <Method for measuring the number average particle size of primary particles of fine particles> The number-average particle size of the primary particles of the microparticles is determined by measurement using the centrifugal sedimentation method. Specifically, 0.01 g of dried microparticles is placed in a 25 ml glass vial, and a solution is prepared by adding 0.2 g of 5% Triton solution and 19.8 g of RO water. Next, the tip of the probe (inner tip) of an ultrasonic disperser is immersed in the solution, and ultrasonic dispersion is carried out at an output of 20 W for 15 minutes to obtain a dispersion. This dispersion is then used to measure the number-average particle size of the primary particles using a centrifugal sedimentation method (CPS Instruments). The number average particle size of the primary particles was measured using a density distribution measuring device DC24000. The disk rotation speed was set to 18,000 rpm, and the true density was 1.3 g / cm. 3 Before measurement, the instrument is calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0102] <Method for measuring the BET specific surface area of ​​fine particles> The BET specific surface area of ​​the microparticles is measured using a Tristar 3000 automatic specific surface area and pore size distribution analyzer (Shimadzu Corporation) by the gas adsorption method, in which nitrogen gas is adsorbed onto the sample surface according to the BET multipoint method. The measurement method follows the operating manual published by Shimadzu Corporation. First, 0.5 g of sample is placed in a sample tube and vacuumed at 100°C for 24 hours. After vacuuming is complete, the sample mass is precisely weighed to obtain the sample. The BET specific surface area can be determined from the obtained sample using the above-mentioned automatic specific surface area and pore size distribution analyzer. The true density value required for measurement is measured using an Accupyc 1330 dry density meter (Shimadzu Corporation).

[0103] <Method for measuring the adhesion rate of external toner additives to toner particles using the water washing method> (Water washing process) A sucrose solution (20.7 g sucrose (Kishida Chemical Co., Ltd.) dissolved in 10.3 g ion-exchanged water) and 6 mL of the surfactant Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were placed in a 30 mL glass vial and mixed thoroughly to prepare a dispersion. The glass vial used can be, for example, a VCV-30 (Nichiden Rika Glass Co., Ltd.) with an outer diameter of 35 mm and a height of 70 mm. 1.0 g of toner is added to this dispersion and allowed to stand until the toner settles naturally to produce a pre-treatment dispersion. This pre-treatment dispersion is shaken in a shaker (YS-8D model, manufactured by Yayoi Co., Ltd.) at a shaking speed of 200 rpm for 5 minutes to detach loosely adhered particles from the toner particle surface. A centrifuge is used to separate the toner with the remaining tightly adhered particles from the detached particles. The centrifugation process is carried out at 3700 rpm for 30 minutes using a small tabletop centrifuge, H-19F (manufactured by Kokusan Co., Ltd.). The toner with the remaining particles is collected by suction filtration, dried, and washed to obtain the toner.

[0104] (Method for measuring the adhesion rate of fine particles) The method for measuring the adhesion rate of fine particles is as follows. First, the amount of fine particles contained in the toner before washing is quantified. The Si element intensity in the toner is measured using a wavelength dispersive X-ray fluorescence analyzer, Axios Advanced (manufactured by PANalytical). Next, the Si element intensity in the toner after washing is measured in the same way. The adhesion rate (%) can be calculated using the following formula. Adhesion rate (%) = (Si element strength in toner after water washing treatment / Si element strength in toner before water washing treatment) x 100

[0105] <Solid 29 Method for measuring the abundance ratios of constituent compounds of fine particles, S3 / A, S4 / A, and S2 / A, using Si-NMR solid 29In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group that binds to Si in the constituent compounds of the particles. By identifying the position of each peak using a standard sample, it is possible to identify the structure that binds to Si. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The M unit structure, The ratio of the peak area of ​​the D unit structure, the T unit structure, and the Q unit structure can be calculated.

[0106] solid 29 The specific conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29 Si 45° Sample tube: zirconia 3.2 mm diameter Sample: Filled in powder form into a test tube Sample rotation speed: 10kHz Relaxation delay: 180s Scan:2000

[0107] After the measurement, the peaks of the multiple silane components of the sample having different substituents and bonding groups are separated into the following M unit structure, D unit structure, T unit structure, and Q unit structure by curve fitting, and the peak area of ​​each is calculated. Curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for the JNM-EX400 manufactured by JEOL Ltd. Click "1D Pro" from the menu icon to load the measurement data. Next, select "Curve fitting function" from "Command" on the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference (composite peak difference) between the composite peak obtained by curve fitting and the peak of the measurement results is minimized. M unit structure: (Ra)(Rb)(Rc)SiO1 / 2 (S1´) D unit structure: (Rd)(Re)Si(O 1 / 2 )2(S2´) T unit structure: RfSi(O 1 / 2 )3(S3´) Q unit structure: Si(O 1 / 2 )4(S4´) The total area of ​​these peaks corresponding to silicon polymers is defined as A, i.e., (S1'+S2'+S3'+S4')=A.

[0108] In the formulae (S1'), (S2'), and (S3'), Ra, Rb, Rc, Rd, Re, and Rf represent silicon-bonded organic groups such as hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl groups and alkoxy groups), halogen atoms, and hydroxy groups. From the peak areas obtained, the peak area S3 corresponding to the structure represented by formula (a), the peak area S4 corresponding to the structure represented by formula (b), and the peak area S2 corresponding to the structure represented by formula (c) are calculated. If it is necessary to confirm the structures in more detail, 29 Along with the Si-NMR measurement results 13 C-NMR and 1 The results of H-NMR may also be used for identification. S3 / A, S4 / A, and S2 / A are calculated from A, S2, S3, and S4 thus determined.

[0109] <Measuring method for surface treatment agents in external toner additives> The surface treatment agent of the external toner additive is analyzed by pyrolysis GC-MS (gas chromatography mass spectrometry). The specific measurement conditions are as follows. Equipment: GC6890A (Agilent), pyrolysis equipment (Japan Analytical Industry Co., Ltd.) Column: HP-5ms 30m Thermal decomposition temperature: 590℃ The surface treatment agent of the external toner additive is identified by identifying the position of each peak in the profile obtained by the measurement using a standard sample.

[0110] <Method for measuring weight average particle size (D4) of toner particles> The weight average particle diameter (D4) of the toner particles is measured using a fine particle size measuring instrument equipped with an aperture tube of 100 μm. Measurements are taken with an effective number of 25,000 measurement channels, and the measurement data is analyzed and calculated using the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) that uses the hole electrical resistance method, and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data.

[0111] The aqueous electrolyte solution used for the measurement is prepared by dissolving special-grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter). Before performing the measurement and analysis, the dedicated software is set up as follows:

[0112] In the dedicated software's "Change Standard Measurement Method (SOM) Screen," set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using a "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the "Flush aperture tube after measurement" box. In the dedicated software's "Pulse to Particle Size Conversion Setting Screen," set the bin spacing to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less. The specific measurement method is as follows.

[0113] (1) Pour approximately 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While ultrasonic waves are irradiated to the electrolyte solution in the beaker in (4), approximately 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, the electrolytic solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to approximately 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4). [Example]

[0114] The present invention will be described in more detail with reference to the following examples, which, however, are not intended to limit the scope of the present invention. Unless otherwise specified, the "parts" in the following formulations are all by mass.

[0115] <Production Example of Toner Additive Particles 1> 1. Hydrolysis process A 200 ml beaker was charged with 43.2 g of RO water and 0.008 g of acetic acid as a catalyst and stirred at 45° C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours to obtain a raw material solution.

[0116] 2. Polycondensation process An alkaline aqueous medium was prepared by adding 68.8 g of RO water, 340.0 g of methanol, and 2.0 g of 25% aqueous ammonia to a 1000 ml beaker and stirring at 30°C. The raw material solution obtained in step 1, Hydrolysis, was added dropwise to this alkaline aqueous medium over 1 minute. After the raw material solution was added dropwise, the mixture was stirred for 1.5 hours while maintaining the temperature at 30°C to allow the polycondensation reaction to proceed, yielding a polycondensation reaction liquid.

[0117] 3.Particleization process 1000g of RO water was placed in a 2000ml beaker, and the polycondensation reaction liquid obtained in 2. Polycondensation Step was added dropwise over 10 minutes while stirring at 25°C. The polycondensation reaction liquid immediately became cloudy upon mixing with the water, yielding a dispersion containing silicon polymer particles with siloxane bonds.

[0118] 4. Hydrophobization process 27.1 g of hexamethyldisilazane as a hydrophobizing agent was added to the dispersion containing the silicon polymer particles having siloxane bonds obtained in the granulation step, and the mixture was stirred at 60°C for 2.5 hours. After leaving the mixture to stand for 5 minutes, the powder that settled to the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain external toner additive particles 1. The number average particle size of the primary particles of the obtained external toner additive particles 1 was 0.12 μm. The physical properties of external toner additive particles 1 are shown in Table 1.

[0119] <Production Example of Toner Additive Particles 2> Toner external additive particles 2 were obtained in the same manner as in the production example for toner external additive particles 1, except that in the hydrolysis step, tetraethoxysilane was changed to 22.0 g, dimethyldimethoxysilane to 32.4 g, the stirring temperature was changed to 40°C, and the amount of 25% ammonia water used in the condensation polymerization step was changed to 2.2 g. The physical properties of the obtained toner external additive particles 2 are shown in Table 1.

[0120] <Production Example of Toner Additive Particles 3> External toner additive particles 3 were obtained in the same manner as in the production example for external toner additive particles 1, except that in the hydrolysis step, tetraethoxysilane was changed to 33.8 g, dimethyldimethoxysilane to 20.6 g, the stirring temperature was changed to 50°C, and the amount of 25% aqueous ammonia used in the condensation polymerization step was changed to 1.8 g. The physical properties of the obtained external toner additive particles 3 are shown in Table 1.

[0121] <Production Example of Toner Additive Particles 4> In the hydrolysis step, the amount of tetraethoxysilane was changed to 14.6 g, the amount of dimethyldimethoxysilane was changed to 30.3 g, and 4.1 g of trimethoxymethylsilane was added. Except for this, the procedure was the same as in the production example for external toner additive particles 3 to obtain external toner additive particles 4. The physical properties of the obtained external toner additive particles 4 are shown in Table 1.

[0122] <Production Example of Toner Additive Particles 5> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 21.2 g and 17.3 g, respectively, and 4.1 g of trimethoxymethylsilane and 11.2 g of triethylmethoxysilane were added, respectively. Except for this, external toner additive particles 5 were obtained in the same manner as in the production example for external toner additive particles 3. The physical properties of the obtained external toner additive particles 5 are shown in Table 1.

[0123] <Production Example of Toner Additive Particles 6> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 36.7 g and 17.3 g, respectively, and 5.4 g of triethylmethoxysilane was added. Except for this, the procedure was the same as in the production example for external toner additive particles 3, to obtain external toner additive particles 6. The physical properties of the obtained external toner additive particles 6 are shown in Table 1.

[0124] <Production Example of Toner Additive Particles 7> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 13.9 g and 22.9 g, respectively, and 4.1 g of trimethoxymethylsilane and 11.2 g of triethylmethoxysilane were added, respectively. Except for this, external toner additive particles 7 were obtained in the same manner as in the production example for external toner additive particles 3. The physical properties of the obtained external toner additive particles 7 are shown in Table 1.

[0125] <Production Example of Toner Additive Particles 8> In the hydrolysis step, the amount of tetraethoxysilane was changed to 37.4 g and the amount of dimethyldimethoxysilane was changed to 21.2 g, and the same procedure as in the production example of external toner additive particles 3 was carried out to obtain external toner additive particles 8. The physical properties of the obtained external toner additive particles 8 are shown in Table 1.

[0126] <Production Example of Toner Additive Particles 9> In the hydrolysis step, the amount of tetraethoxysilane was changed to 13.9 g, the amount of dimethyldimethoxysilane was changed to 30.7 g, and 4.1 g of trimethoxymethylsilane was added. Except for this, the procedure was the same as in the production example for external toner additive particles 3, to obtain external toner additive particles 9. The physical properties of the obtained external toner additive particles 9 are shown in Table 1.

[0127] <Production Example of Toner Additive Particles 10> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 13.9 g and 16.9 g, respectively, and 4.1 g of trimethoxymethylsilane and 17.1 g of triethylmethoxysilane were added, respectively. Except for this, the procedure was the same as in the production example of external toner additive particles 3, to obtain external toner additive particles 10. The physical properties of the obtained external toner additive particles 10 are shown in Table 1.

[0128] <Production Example of Toner Additive Particles 11> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 14.6 g and 16.9 g, respectively, and 9.9 g of trimethoxymethylsilane and 11.8 g of triethylmethoxysilane were added. Except for this, the procedure was the same as in the production example for toner external additive particles 3, to obtain toner external additive particles 11. The physical properties of the obtained toner external additive particles 11 are shown in Table 1.

[0129] <Production Example of Toner Additive Particles 12> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 13.9 g and 16.9 g, respectively, and 21.5 g of trimethoxymethylsilane and 1.1 g of triethylmethoxysilane were added, respectively. Except for this, the procedure was the same as in the production example for external toner additive particles 3, to obtain external toner additive particles 12. The physical properties of the obtained external toner additive particles 12 are shown in Table 1.

[0130] <Production Example of Toner Additive Particles 13> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 13.9 g and 16.9 g, respectively, and 22.0 g of trimethoxymethylsilane and 0.5 g of triethylmethoxysilane were added, respectively. Except for this, the procedure was the same as in the production example for external toner additive particles 3, to obtain external toner additive particles 13. The physical properties of the obtained external toner additive particles 13 are shown in Table 1.

[0131] <Production Example of Toner Additive Particles 14> Toner external additive particles 14 were obtained in the same manner as in the production example of toner external additive particles 13, except that the hydrophobizing agent used in the hydrophobizing step was changed to octamethylcyclotetrasiloxane. The physical properties of the obtained toner external additive particles 14 are shown in Table 1.

[0132] <Production Example of Toner Additive Particles 15> In the hydrophobizing step, the hydrophobizing agent used was changed to chlorotrimethylsilane, and the same procedure as in the production example of the toner external additive particle 13 was repeated to obtain the toner external additive particle 15. The physical properties of the obtained toner external additive particle 15 are shown in Table 1.

[0133] <Production Example of Toner Additive Particles 16> In the hydrophobizing step, the hydrophobizing agent used was changed to trifluoropropyltrimethoxysilane, and the same procedure as in the production example of the toner external additive particle 13 was repeated to obtain the toner external additive particle 16. The physical properties of the obtained toner external additive particle 16 are shown in Table 1.

[0134] <Production Example of Toner Additive Particles 17> In the hydrophobizing step, the hydrophobizing agent used was changed to dimethyl silicone oil, and the same procedure as in the production example of the toner external additive particles 13 was repeated to obtain the toner external additive particles 17. The physical properties of the obtained toner external additive particles 17 are shown in Table 1.

[0135] <Production Example of Toner Additive Particles 18> Except for not using a hydrophobizing agent in the hydrophobizing step, the same procedure as in the production example of the toner external additive particles 13 was carried out to obtain the toner external additive particles 18. The physical properties of the obtained toner external additive particles 18 are shown in Table 1.

[0136] <Production Example of Toner Additive Particles 19> Except for changing the stirring temperature in the hydrolysis step to 40°C and changing the amount of 25% aqueous ammonia used in the polycondensation step to 2.3 g, the same procedure as in the production example for external toner additive particles 18 was carried out to obtain external toner additive particles 19. The physical properties of the obtained external toner additive particles 19 are shown in Table 1.

[0137] <Production Example of Toner Additive Particles 20> Toner external additive particles 20 were obtained in the same manner as in the production example for toner external additive particles 18, except that in the hydrolysis step, the stirring temperature was changed to 50°C and the amount of 25% ammonia water used in the polycondensation step was changed to 1.3 g. The physical properties of the obtained toner external additive particles 20 are shown in Table 1.

[0138] <Production Example of Toner Additive Particles 21> Except for changing the amount of 25% aqueous ammonia used in the polycondensation step to 2.4 g, the same procedure as in the production example of external toner additive particles 19 was carried out to obtain external toner additive particles 21. The physical properties of the obtained external toner additive particles 21 are shown in Table 1.

[0139] <Production Example of Toner Additive Particles 22> Except for changing the amount of 25% aqueous ammonia used in the polycondensation step to 1.2 g, the same procedure as in the production example of external toner additive particles 20 was carried out to obtain external toner additive particles 22. The physical properties of the obtained external toner additive particles 22 are shown in Table 1.

[0140] <Production Example of Toner Additive Particles 23> Except for changing the amount of 25% aqueous ammonia used in the polycondensation step to 1.0 g, the same procedure as in the production example of external toner additive particles 20 was repeated to obtain external toner additive particles 23. The physical properties of the obtained external toner additive particles 23 are shown in Table 1.

[0141] <Production Example of Toner Additive Particles 24> Toner external additive particles 24 were obtained in the same manner as in the production example for toner external additive particles 19, except that the amount of 25% ammonia water used in the polycondensation step was changed to 3.0 g. The physical properties of the agent particles 24 are shown in Table 1.

[0142] <Production Example of Toner Additive Particles 25> In the hydrolysis step, the amount of tetraethoxysilane was changed to 13.9 g, the amount of dimethyldimethoxysilane was changed to 13.0 g, and 27.8 g of trimethoxymethylsilane was added, but no triethylmethoxysilane was added, and the same procedure as in the production example for external toner additive particles 24 was repeated to obtain external toner additive particles 25. The physical properties of the obtained external toner additive particles 25 are shown in Table 1.

[0143] <Production Example of Toner Additive Particles 26> In the hydrolysis step, the amount of tetraethoxysilane was changed to 13.9 g, the amount of dimethyldimethoxysilane was changed to 8.6 g, and 33.6 g of trimethoxymethylsilane was added. Except for this, the same procedure as in the production example for external toner additive particles 25 was carried out to obtain external toner additive particles 26. The physical properties of the obtained external toner additive particles 26 are shown in Table 1.

[0144] <Production Example of Toner Additive Particles 27> Toner external additive particles 27 were obtained in the same manner as in the production example for toner external additive particles 26, except that in the condensation polymerization step, the stirring temperature was changed to 23° C. The physical properties of the obtained toner external additive particles 27 are shown in Table 1.

[0145] <Production Example of Toner Additive Particles 28> In the hydrolysis step, tetraethoxysilane and dimethyldimethoxysilane were not added, and instead 54.4 g of trimethoxymethylsilane was added, and the stirring temperature was changed to 30°C and the stirring time to 0.5 hours, but the same procedure as in the production example of external toner additive particles 1 was repeated to obtain external toner additive particles 28. The physical properties of the obtained external toner additive particles 28 are shown in Table 1.

[0146] <Production Example of Toner Additive Particles 29> Except for not using a hydrophobizing agent in the hydrophobizing step, the same procedure as in the production example of the toner external additive particles 28 was carried out to obtain the toner external additive particles 29. The physical properties of the obtained toner external additive particles 29 are shown in Table 1.

[0147] <Production Example of Toner Additive Particles 30> A 2000 ml beaker was charged with 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia. The solution was adjusted to 70°C, and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours with stirring. After the addition was complete, stirring was continued for another 0.5 hours to allow hydrolysis to occur, yielding a dispersion of silicon polymer particles having siloxane bonds.

[0148] To the dispersion of silicon polymer particles having siloxane bonds obtained in the above step, 95.0 g of hexamethyldisilazane was added at room temperature, and the dispersion was then heated to 50-60°C and stirred for 3.0 hours. The powder in the dispersion was recovered by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain external toner additive particles 30. The physical properties of the obtained external toner additive particles 30 are shown in Table 1.

[0149] <Production Example of Toner Additive Particles 31> External toner additive particles 31 were obtained in the same manner as in the production example of external toner additive particles 30, except that tetraethoxysilane was changed to 208.8 g and 23.2 g of trimethoxymethylsilane was added. The physical properties of the obtained external toner additive particles 31 are shown in Table 1.

[0150] <Production Example of Toner Additive Particles 32> External toner additive particles 32 were obtained in the same manner as in the production example for external toner additive particles 1, except that in the hydrolysis step, 7.3 g of tetraethoxysilane, 21.6 g of dimethyldimethoxysilane, and 21.5 g of trimethoxymethylsilane were added, and the stirring temperature was changed to 30° C. and the stirring time to 0.5 hours. The physical properties of the obtained external toner additive particles 32 are shown in Table 1.

[0151] <Production Example of Toner Additive Particles 33> In the hydrolysis step, 29.3 g of tetraethoxysilane, 4.3 g of dimethyldimethoxysilane, and 27.2 g of trimethoxymethylsilane were added, and the stirring temperature was changed to 30° C. and the stirring time to 0.5 hours, and the same procedure as in the production example of external toner additive particles 1 was repeated to obtain external toner additive particles 33. The physical properties of the obtained external toner additive particles 33 are shown in Table 1.

[0152] <Production Example of Toner Additive Particles 34> Except for changing the amount of 25% aqueous ammonia used in the polycondensation step to 0.9 g, the same procedure as in the production example of external toner additive particles 20 was carried out to obtain external toner additive particles 34. The physical properties of the obtained external toner additive particles 34 are shown in Table 1.

[0153] <Production Example of Toner Additive Particles 35> Except for changing the amount of 25% aqueous ammonia used in the polycondensation step to 3.2 g, the same procedure as in the production example of external toner additive particles 27 was carried out to obtain external toner additive particles 35. The physical properties of the obtained external toner additive particles 35 are shown in Table 1.

[0154] [Table 1] In the table, "SiOH content" refers to the amount of silanol groups per gram of microparticles, "particle size" refers to the number-average particle size of primary particles, "BET" refers to the BET specific surface area, "D4" refers to octamethylcyclotetrasiloxane, "chlorosilane" refers to chlorotrimethylsilane, "fluorine silane" refers to trifluoropropyltrimethoxysilane, and "silicone oil" refers to dimethylsilicone oil.

[0155] <Production Example of Polyester Resin A1> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mole parts) Terephthalic acid (TPA) 25.0 parts (0.145 mole parts) Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 4 hours at 200°C while stirring (first reaction step). Then, 1.2 parts (0.006 moles) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react for 1 hour at 180°C (second reaction step), yielding polyester resin A1.

[0156] <Production Example of Polyester Resin A2> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 mole parts) Terephthalic acid 24.1 parts (0.145 mole parts) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, a stirring rod, a condenser, and a nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 2 hours at 200°C while stirring. Subsequently, 5.8 parts (0.030 moles) of trimellitic anhydride was added, and the mixture was allowed to react for 10 hours at 180°C, yielding Polyester Resin A2.

[0157] <Production Example of Toner Particle 1> Polyester resin A1 70.0 parts Polyester resin A2 30.0 parts Fischer-Tropsch wax (maximum endothermic peak temperature 78°C) 5.0 parts CI Pigment Blue 15:3 5.0 parts 0.1 parts of 3,5-di-t-butylsalicylic acid aluminum compound The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at 125°C and 300 rpm. The resulting mixture was cooled and coarsely crushed to a diameter of 1 mm or less using a hammer mill. The resulting coarsely crushed material was then finely crushed in a mechanical crusher (T-250, manufactured by Freund Turbo Corporation).

[0158] Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were a classification rotor rotation speed of 50.0 s -1 The resulting toner particles 1 had a weight average particle size (D4) of 5.9 μm.

[0159] <Toner 1 manufacturing example> 100 parts of toner particles Toner additive particles 1 5.0 parts The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s -1 The mixture was mixed for a rotation time of 10 minutes to obtain toner particle mixture 1.

[0160] (Heat treatment process) The obtained toner particle mixture 1 was subjected to heat treatment by the surface treatment device shown in FIG. 1 to obtain toner 1. The physical properties of toner 1 are shown in Table 2. The operating conditions for the heat treatment were: feed amount = 2 kg / hr, hot air temperature = 150°C, hot air flow rate = 6m 3 / min., cold air temperature = -5℃, cold air flow rate = 2.5m 3 / min., Blower air volume = 11m 3 / min., injection air flow rate = 1m 3 / min.

[0161] <Production Examples of Toners 2 to 42> Toners 2 to 42 were obtained in the same manner as in the production example of Toner 1, except that the external toner additive, whether or not the hot air treatment step was performed, and the hot air temperature in the heat treatment step were changed to those shown in Table 2. The physical properties of Toners 2 to 42 are shown in Table 2.

[0162] [Table 2] In the table, the amount added is the number of parts per 100 parts of toner particles.

[0163] <Carrier 1 manufacturing example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength under a magnetic field of (1000 / 4π(kA / m) 65Am 2 / kg) of magnetite2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles.

[0164] Phenol: 10% by weight Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26 mass% 100 parts of the above material, 5 parts of a 28% by weight aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85°C over 30 minutes and maintained at that temperature while stirring and mixing. The polymerization reaction was carried out for 3 hours, resulting in hardening of the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain magnetic material-dispersed spherical carrier 1. The volume-based 50% particle size (D50) was 34.2 μm.

[0165] <Manufacturing example of two-component developer 1> To 92.0 parts of Carrier 1, 8.0 parts of Toner 1 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain Two-Component Developer 1.

[0166] <Production Examples of Two-Component Developers 2 to 42> Two-component developers 2 to 42 were obtained by carrying out production in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3.

[0167] [Table 3]

[0168] <Toner evaluation method> (Measurement of image density difference) The image forming apparatus was a Canon full-color copier, imagePress C800, and the above two-component developer was placed in the cyan developer of the image forming apparatus, and the above toner was placed in the cyan toner container, and the evaluation described below was carried out. The modification was to remove the mechanism that discharges excess magnetic carrier from the developer. The evaluation paper was plain paper GF-C. 081(A4, basis weight 81.4g / m 2 (sold by Canon Marketing Japan Inc.) was used.

[0169] The amount of toner on the paper in a FFh image (solid image) is 0.45 mg / cm 2 The settings were adjusted so that the result was as follows: FFh is the hexadecimal representation of 256 gradations, with 00h being the first gradation of 256 gradations (white background) and FF being the 256th gradation of 256 gradations (solid area). First, an image output test of 1,000 sheets was conducted at an image ratio of 1%. During the continuous printing of 1,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet.

[0170] After that, an image output test of 1,000 sheets was conducted at an image ratio of 80%. During the continuous printing of 1,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet. The image density of the 1,000th sheet printed at an image ratio of 1% was taken as the initial density, and the density of the 1,000th image printed at an image ratio of 80% was measured and evaluated.

[0171] The above tests were conducted under normal temperature and humidity conditions (N / N; temperature 25°C, relative humidity 55%), high temperature and humidity conditions (H / H; temperature 30°C, relative humidity 80%), and low temperature and humidity conditions (L / L; temperature 15°C, relative humidity 10%). Using an X-Rite color reflection densitometer (500 series, manufactured by X-Rite), the initial density and the density of the 1,000th image printed at an image ratio of 80% were measured, and the difference Δ was used to rank the images according to the following criteria. A score of D or higher was considered good. (Evaluation standard: Image density difference Δ) A: Less than 0.02 B: 0.02 or more and less than 0.05 C: 0.05 or more and less than 0.10 D: 0.10 or more and less than 0.15 E: 0.15 or more

[0172] (Evaluation of image density uniformity) After printing the 1,000th sheet at the 80% image ratio, a solid image was output, and a 2cm square image was captured using a digital microscope. The captured image was converted to 8-bit grayscale using Image-J, and then a density histogram was measured and its standard deviation was calculated. The standard deviation was ranked according to the following evaluation criteria. The above test was conducted under normal temperature and humidity conditions (N / N; temperature 25°C, relative humidity 55%), high temperature and humidity conditions (H / H; temperature 30°C, relative humidity 80%), and low temperature and humidity conditions (L / L; temperature 15°C, relative humidity 10%). A grade of D or higher was considered good. A: Standard deviation less than 2.0 B: Standard deviation 2.0 or more and less than 4.0 C: Standard deviation 4.0 or more and less than 5.0 D: Standard deviation 5.0 or more and less than 6.0 E: Standard deviation 6.0 or more

[0173] (image quality) After printing the 1,000th image and solid image at the above 80% image ratio, a 1-dot, 1-space vertical line image was output. The Blur value (a numerical value that indicates the degree of blurring of lines as defined by ISO 13660) was used as an index for evaluating image quality. The Blur value was measured using a personal IAS (Image Analysis System) (manufactured by QEA). The above test was conducted under normal temperature and humidity conditions (N / N; temperature 25°C, relative humidity 55%), high temperature and humidity conditions (H / H; temperature 30°C, relative humidity 80%), and low temperature and humidity conditions (L / L; temperature 15°C, relative humidity 10%). The obtained Blur values ​​were evaluated according to the following evaluation criteria. A grade of D or above was considered good. A: Blur value less than 35 μm B: Blur value 35 μm or more and less than 38 μm C: Blur value 38μm or more and less than 41μm D: Blur value 41 μm or more and less than 44 μm E: Blur value 44μm or more

[0174] <Evaluation Results of Examples 1 to 34> The evaluation results of Examples 1 to 34 are shown in Table 4. Examples 14 to 34 were evaluated as reference examples.

[0175] [Table 4] In the table, SD indicates standard deviation, and Bl indicates the value of Blur (μm). [Explanation of symbols]

[0176] 1. Raw material constant quantity supply means, 2. Compressed gas flow rate adjustment means, 3. Inlet pipe, 4. Protruding member, 5 . Supply pipe, 6. Treatment chamber, 7. Hot air supply means, 8. Cold air supply means, 9. Regulating means, 10. Recovery means, 11. Hot air supply means outlet, 12. Distribution member, 13. Swirling member, 14. Powder particle supply port

Claims

1. Microparticles of a silicon polymer having siloxane bonds and silanol groups, the water adsorption amount of the microparticles at a temperature of 30°C and a humidity of 80% RH is 1.0 mg / g or more and 22.0 mg / g or less; the amount of silanol groups in the fine particles measured by a titration method using KOH is 0.012 mmol / g or more and 0.120 mmol / g or less, the number average particle size of the primary particles of the fine particles is 0.05 μm or more and 0.30 μm or less; In a chart obtained by measuring the 29Si-NMR of the microparticles, when the total peak area corresponding to the silicon polymer is A, the peak area corresponding to the structure represented by the following formula (a) is S3, the peak area corresponding to the structure represented by the following formula (b) is S4, and the peak area corresponding to the structure represented by the following formula (c) is S2, The particles are characterized in that A, S3, S4, and S2 satisfy the following formulas (1), (2), and (3): S3 / A≦0.40...(1) 0.20≦S4 / A≦0.50 (2) 0.40≦S2 / A≦0.70 (3) In formula (a), R 1 represents an alkyl group having 1 to 6 carbon atoms. In formula (c), R 2 and R 3 each independently represent an alkyl group having 1 to 6 carbon atoms.

2. The BET specific surface area of ​​the fine particles is 30 m ２ / g or more 250m ２ The fine particles according to claim 1, wherein the particle size is 1 / g or less.

3. 3. The fine particles according to claim 1, wherein the fine particles are surface-treated with at least one compound selected from the group consisting of alkylsilazanes, cyclic dimethylpolysiloxanes, chlorosilanes, fluorosilanes, and silicone oils.

4. The microparticles according to any one of claims 1 to 3, wherein the silicon polymer is a condensation polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (A): In formula (A), R １２ , R １３ , R １４ and R １５ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a reactive group, and the reactive group represents a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group having 1 to 6 carbon atoms. １２ , R １３ , R １４ and R １５ At least one of the groups is the reactive group.

5. An external toner additive comprising the fine particles according to any one of claims 1 to 4.

6. A toner having toner particles and an external toner additive, the toner particles contain a binder resin, A toner, wherein the external toner additive is the external toner additive according to claim 5 .

7. 7. The toner according to claim 6, wherein the content of the external toner additive in the toner is 0.1 parts by mass to 20.0 parts by mass with respect to 100 parts by mass of the toner particles.

8. 8. The toner according to claim 6, wherein when the toner is dispersed in an aqueous medium containing a surfactant and sucrose, the dispersion is shaken in a shaker, and then centrifuged, a rate of adhesion of the external toner additive to the toner particles is 20% or more.

9. A two-component developer having a toner and a magnetic carrier, A two-component developer, wherein the toner is the toner according to any one of claims 6 to 8.

10. A method for producing the toner according to any one of claims 6 to 8, comprising the steps of: a mixing step of mixing the toner particles with the external toner additive to obtain a toner particle mixture; and a heat treatment step of heat treating the toner particle mixture; A method for producing a toner having the formula:

Images